EP0142103B1 - Method for conducting a chemical process in a packed multi-step tubular reactor - Google Patents

Method for conducting a chemical process in a packed multi-step tubular reactor Download PDF

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Publication number
EP0142103B1
EP0142103B1 EP84113109A EP84113109A EP0142103B1 EP 0142103 B1 EP0142103 B1 EP 0142103B1 EP 84113109 A EP84113109 A EP 84113109A EP 84113109 A EP84113109 A EP 84113109A EP 0142103 B1 EP0142103 B1 EP 0142103B1
Authority
EP
European Patent Office
Prior art keywords
liquid
tubes
vessel
product
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84113109A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0142103A1 (en
Inventor
Carlo Galileo Alesandrini, Jr.
Louie Akos Nady
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stauffer Chemical Co
Original Assignee
Stauffer Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stauffer Chemical Co filed Critical Stauffer Chemical Co
Priority to AT84113109T priority Critical patent/ATE27411T1/de
Publication of EP0142103A1 publication Critical patent/EP0142103A1/en
Application granted granted Critical
Publication of EP0142103B1 publication Critical patent/EP0142103B1/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to an improved method for conducting a chemical process in a multi-tubular vessel containing a plurality of packed vertically arranged tubes.
  • this invention relates to an improvement in conducting a process in such a vessel in which a feed which contains at least one liquid is introduced into the vessel and in which at least one liquid product and at least one gaseous product are obtained.
  • the gaseous product may be, for instance, a gas which had been also introduced as a feed or which was dissolved in the liquid and is recovered as a vapor from the vessel, a liquid introduced as feed which becomes vaporized during the conduct of the process, or a gas produced by a chemical reaction of the liquid feed or between the liquid feed and another reactant introduced.
  • the liquid product obtained may be a portion of the liquid feed which, for instance, was not reacted in the vessel, or a liquid product obtained by reaction of the liquid feed with another reactant.
  • Examples of processes which may be generally carried out in packed multi-tubular reactors are those which are exothermic or endothermic such as hydrocarbon reforming, cyclization, dehydrogenation, desulfurization and dehydration.
  • the packing may include one or more catalysts known to effectuate such reactions.
  • heat transfer to or from the tubes is accomplished through the use of gaseous or liquid heat transfer fluid in the shell space surrounding the tubes.
  • a liquid feed is introduced in line 1 into a vessel or reactor 2 which contains a plurality of vertically arranged packed tubes 3.
  • the liquid feed optionally together with other feeds, is forced to flow downwardly through the tubes and the packing contained therein, and all products, liquid and gaseous, are removed from the lower portion of vessel 2 via line 4.
  • the liquid and gaseous products contained in line 4 are then sent for further processing.
  • One example of such is shown in Figure 1, in which the liquid and gaseous products in line 4 are introduced into a liquid/gas separator 5, with gaseous product being removed via line 6 and liquid product via line 7.
  • FIG. 2 A second method of operation of such processes is depicted in Figure 2.
  • a feed containing at least one liquid is introduced via line 10 into a vessel or reactor 11 containing a plurality of vertically arranged packed tubes 12.
  • the feed, and products produced therefrom are forced to flow upwardly through the tubes 12 and are removed at the upper portion of the vessel in line 13.
  • these products in line 13 are transmitted for further processing, for instance, passed into a liquid/gas separator 14 from which gaseous product is removed via line 15 and liquid product in line 16.
  • the tubes when operating with forced downflow and removal of all products from the lower portion of the vessel as in Figure 1, the tubes will function as miniature trickle bed reactors because of the gases produced. This results in considerably less efficient transfer of heat to or from the tubes than is desired.
  • liquid may flow more rapidly into and down the tubes located closer to the liquid inlet or inlets than tubes located further away. In such operations, therefore, there may be a lack of uniformity of conditions from tube to tube, and a somewhat inefficient use of tubes, since some will carry more of the process load than others. Transfer of heat to or from tubes will similarly be nonuniform and thus generally less efficient. This may result in poor control of this reaction; the yield may be reduced, and/or undesired by-products may be formed.
  • the process to be conducted is one which involves a comparatively long reaction, the reactants may flow through the tubes too quickly, and reaction may not be complete.
  • a secondary objective of this invention is to provide such an improved process for use in the production of chlorothioformates which are liquids, by reaction of a liquid mercaptan with phosgene, which may be in liquid or gaseous form, and in which gaseous products such as hydrogen chloride and optionally phosgene are obtained.
  • This invention comprises a method for conducting a liquid phase chemical process in which a feed containing at least one liquid is introduced into a vessel containing a plurality of packed, vertically arranged tubes, and in which at least one liquid product and at least one gaseous product are obtained, comprising:
  • the process is carried out in a vertically situated vessel or reactor, designated generally as 21.
  • a liquid/vapor disengagement zone 23 In the upper portion of the vessel 21 is a liquid/vapor disengagement zone 23.
  • a plurality of vertically arranged tubes 22 Within the vessel are situated a plurality of vertically arranged tubes 22 which are held in place by upper and lower tube sheets 22a and 22b, respectively.
  • the tubes are packed essentially from top to bottom with a particulate solid material.
  • the particulate material may contain catalytic material, either perse, or supported on an inert particulate support.
  • the particulate material may be some inert material which enhances in some other way the conduct of the process, for instance a packing, an adsorbent, an absorbent, an ion exchange resin, etc.
  • a liquid feed which may be a single liquid, a mixture of liquids, or a mixture of one or more liquids with one or more gases, is introduced into the upper portion of the vessel 21 via line 20, above the upper tube sheet 22a.
  • the liquid, together with such other feeds as may be introduced, is caused to flow downwardly through the packed tubes 22.
  • a liquid product which may comprise an originally fed liquid, a liquid produced by a chemical reaction within the packed tubes 22, or a mixture of two or more such liquids, is withdrawn from the lower portion of the vessel, below the lower tube sheet 22b, via line 25 which includes a vertical upleg 26.
  • the liquid product in line 25 is passed to a downstream section 27 for further processing, such as conducting a further reaction, or separating liquid products.
  • a final desired liquid product is obtained and withdrawn via line 28.
  • a gaseous product which may be a gas originally introduced along with the liquid feed in line 20 (e.g., dissolved in the liquid), a vaporized liquid introduced through line 20, a gaseous product produced by a chemical reaction in the packed tubes 22, or a mixture of two or more of the above, is withdrawn from the upper portion of reactor 21 in line 24, and may similarly be passed downstream for further processing as desired. Most preferably, the gas is withdrawn at a point above the liquid inlet or inlets.
  • the process according to the present invention is carried out continuously, with continuous introduction of a liquid feed in line 20, continuous withdrawal of a liquid product in line 25, and continuous withdrawal of a gaseous product in line 24.
  • the process may also be carried out batch-wise.
  • the conduct of the process is accomplished in the liquid phase, by maintaining the packed tubes 22 essentially uniformly filled with liquid, by causing the reactor to become flooded with liquid, while the gaseous product or products, whether originally introduced, or generated in the packed tubes, passes upwardly through the liquid and is removed as overhead from the vessel.
  • the liquid level in the vessel is maintained above the upper ends of the tubes substantially throughout the interior of the vessel in order to keep the tubes filled with liquid.
  • the flooding of the tubes with liquid is accomplished by controlling the removal of liquid from the reactor in line 25 to provide a sufficient back pressure on the liquid, causing the liquid to back up and overflow through the upper ends of the tubes 22 into the space above tube sheet 22a.
  • the same back pressure causes the gaseous product to flow upwardly through the tubes rather than cocurrently downward with the liquid, as in the prior art (Cf. Fig. I).
  • the inlet through which the liquid is introduced in line 20 may be above or below the liquid surface in the upper portion of vessel 21. Most preferably, for best distribution, the liquid in line 20 is introduced into the vessel through a multiplicity of inlets arranged circumferentially around the upper portion of the vessel, above the upper tube sheet.
  • the removal of the liquid in line 25 may be controlled by a number of means, including loop seals, preferably by a regulated upleg 26 on the liquid take-off line 25.
  • control of the liquid removal in line 25 is performed in response to signals from one or more sensing devices located in the upper portion of the vessel 21, above the upper tube sheet, which indicate the height of the liquid level in this upper portion.
  • the liquid removal in line 25 may be controlled automatically by computer process controls (not shown), in response to such signals. Regulation of the liquid in this manner can be performed by conventional flow regulators, including loop seals, valves, etc., installed in line 25.
  • Another means of controlling the liquid is to regulate the liquid in the upleg mentioned above at a high enough level so that the value representing the product of liquid density multiplied by liquid height in upleg 26 is equal to the value of liquid density multiplied by liquid height in tubes 22.
  • the process may be started up by first introducing liquid into the vessel through line 20 while maintaining a controlled removal of liquid (unprocessed) in line 25 until the liquid level in the vessel is above the upper tube sheet. At this point, a reaction or other process may be commenced by, for instance, increasing the temperature within the reactor, or introducing an additional reactant into the feed.
  • Removing the liquid in a controlled manner as described results not only in flooding the tubes with liquid, thus maintaining uniformity of flow, but in causing the gas product to pass upwards through the tubes and out of the reactor via line 24 rather than downwardly or along with the liquid in the outlet line 25.
  • Such control, and causation of the gas flow upwards results in a more uniform and thorough mixing of liquid and gas as well as more ready separation of the two in the vessel 21, facilitating the separate removal of liquid and gaseous products from the vessel. It further provides good heat transfer throughout the tubular zone.
  • the chloroformates desired are those having the formula RSCOCI in which R is alkyl, fewer cycloalkyl, lower cycloalkyl-methyl, lower alkenyl, phenyl, chloro-substituted phenyl, benzyl, or chloro-substituted alkyl in which the chloro substituent is situated at least as far as the gamma carbon atom, with respect to the sulfur atom.
  • Process conditions for the production of such compounds by reaction of mercaptans with phosgene are contained in U.S. Patent 4,119,659.
  • the tubes 22 are packed with activated carbon catalyst of an appropriate size such that each tube functions in the conventional manner as a miniature packed bed reactor.
  • the liquid feed in line 20 is introduced into the upper portion 23 of reactor 21, above the upper tube sheet, preferably through a plurality of inlets arranged circumferentially around the reactor.
  • the liquid is caused to flow downwardly through the tubes, while a pool of liquid is maintained in the upper portion of reactor 21 above the upper ends of tube 22 and the upper tube sheet 22a.
  • mercaptan and phosgene react, resulting in the production of liquid ethyl chlorothioformate and gaseous hydrogen chloride. Additionally, some phosgene may be vaporized in the tubes.
  • the gaseous product or products formed pass upwardly through the tubes 22, through the vapor/liquid disengagement zone 23, and are removed from the reactor in overhead line 24. These gaseous products are then passed downstream for further processing such as recovery of hydrogen chloride produced in the reaction, recovery of phosgene, and gaseous emissions control.
  • the reactor 21 is maintained at an average outlet temperature of generally between 0° and 70°C., and preferably between 0° and 50°C. Most preferably the temperature is between 50° and 65°C. at the outlet and between 15°C. and 40°C., at the inlet.
  • the pressure may range between about 0 and 10,3 bar (150 psig), preferably between 0 and 3,5 bar (50 psig); and most preferably between 2,1 bar (30 psig) and 2,5 bar (36 psig).
  • the rate of removal of liquid product in line 25 is controlled, for instance by a liquid level control or by passing the liquid product in line 25 through an upleg 26 which extends high enough to cause sufficient back pressure on the reactor to maintain the pool of liquid in the upper portion of reactor 21 above the upper ends of substantially all the tubes.
  • the liquid product in line 26 is then passed to downstream apparatus 27.
  • equipment 27 may be a second reactor for further reaction of ethyl mercaptan with phosgene, as shown in U.S. Patent 4,119,659. Products are removed in line 28 and passed downstream for separation or further treatment. If, on the other hand, reaction is sufficiently complete, equipment 27 may be a separator in which the product ethyl chlorothioformate, is removed from the other materials in line 26. These other materials, comprising primarily unreacted phosgene and/or ethyl mercaptan may then be recycled in line 29 to join the liquid in line 20.
  • a reactor system is utilized as shown in Figure 2, having a capacity for production of about 16800 kg (37,000 lbs.) per day of ethyl chlorothioformate.
  • the reactor is a tubular upflow reactor, with the tubes packed with activated carbon catalyst.
  • a reactor is utilized as in Figure 3, according to this invention.
  • This reactor has the same number of tubes, is the same size and contains the same amount of carbon catalyst as the reactor in Example 1. However, the capacity of production for this reactor is about 25 800 kg (57,000 lbs.) per day of ethyl chlorothioformate.
  • This reactor is operated in the flooded downflow mode with the tubes packed with activated carbon catalysts.
  • Into the reactor corresponding to the reactor 21 of Figure 3, are fed 10,1 kmol/h (22.4 lb.-moles/h) of phosgene and 9,2 kmol/h (20.4 lb.-moles/h) of ethyl mercaptan.
  • the reactor is operated at an inlet temperature of 15 ⁇ 40°C,. and an outlet temperature 50-65°C, and an outlet pressure of 2,1-2,5-bar (30-36 psig).
  • Conversion of ethyl mercaptan to the chlorothioformate is about 90%. After removing the unreacted raw materials the product is produced in 98% purity, containing 0.5% diethyl disulfide and less than 1% diethyl dithiocarbonate.
  • a two-reactor system is utilized as shown in Figure 6, having a capacity for production of about 77,500 kg (171,000 lb. per day of ethyl chlorothioformate.
  • the first reactor is a tubular flooded downflow reactor, with the tubes packed with activated carbon catalyst.
  • the second reactor is a packed bed reactor containing a bed of carbon catalyst and is operated as an upflow reactor.
  • Into the first reactor corresponding to reactor 21 are fed 30,4 kmol/h (67.2 lb.-moles/h) of phosgene and 27,7 kmol/b (61.2 lb.-moles/h) of ethyl mercaptan.
  • the reactor is operated at an inlet temperature of 15-40°C., an outlet temperature of 50-65°C., and an outlet pressure of 2,1-2,5 bar (30-36 psig).
  • the products from the first reactor are fed into the lower portion of the second reactor 27 together with a recycle stream containing 14,5 kmol/h (32.1 lb.-moles/h) of phosgene and 6,4 kmol/h (14.1 Ib-moles/h) of ethyl chlorothioformate.
  • the second reactor is operated in an inlet temperature of 18-26°C., an outlet temperature of 33-49°C. and an outlet pressure of 1,6-1,9 bar (24-28 psig).
  • Conversion of ethyl mercaptan to the chlorothioformate is 94%.
  • the product is produced in 98% purity, containing 0.5% diethyl disulfide and less than 1% diethyl dithiocarbonate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP84113109A 1983-11-07 1984-10-31 Method for conducting a chemical process in a packed multi-step tubular reactor Expired EP0142103B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84113109T ATE27411T1 (de) 1983-11-07 1984-10-31 Verfahren zur durchfuehrung eines chemischen verfahrens in einem gefuellten mehrstufigen tubulaeren reaktor.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US549150 1983-11-07
US06/549,150 US4551325A (en) 1983-11-07 1983-11-07 Method for conducting a chemical process in a packed multi-tubular reactor

Publications (2)

Publication Number Publication Date
EP0142103A1 EP0142103A1 (en) 1985-05-22
EP0142103B1 true EP0142103B1 (en) 1987-05-27

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Family Applications (1)

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EP84113109A Expired EP0142103B1 (en) 1983-11-07 1984-10-31 Method for conducting a chemical process in a packed multi-step tubular reactor

Country Status (25)

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US (1) US4551325A (es)
EP (1) EP0142103B1 (es)
JP (1) JPS60118231A (es)
KR (1) KR900008117B1 (es)
AR (1) AR242134A1 (es)
AT (1) ATE27411T1 (es)
AU (1) AU568692B2 (es)
BR (1) BR8405634A (es)
CA (1) CA1212524A (es)
DD (1) DD231296A5 (es)
DE (1) DE3463902D1 (es)
DK (1) DK158875C (es)
ES (1) ES537412A0 (es)
HU (1) HU197855B (es)
IL (1) IL73436A (es)
IN (1) IN162240B (es)
MX (1) MX165645B (es)
NZ (1) NZ210119A (es)
PH (1) PH21356A (es)
PL (1) PL144228B1 (es)
PT (1) PT79462A (es)
RO (1) RO90519A (es)
SU (1) SU1376938A3 (es)
YU (1) YU45674B (es)
ZA (1) ZA848654B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004020082A1 (en) * 2002-09-01 2004-03-11 The University Of Waikato Reaction process

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
GB2177318B (en) * 1985-07-02 1989-01-18 Shell Int Research Catalytic conversion of gas or liquid in a multitube reactor
NL9002322A (nl) * 1990-10-24 1992-05-18 Heineken Technische Beheer Bv Werkwijze voor het winnen van in hoofdzaak zuiver co2 uit een fermentatie gas.
US5601797A (en) * 1992-08-10 1997-02-11 Glitsch, Inc. Liquid-phase catalyst-assembly for chemical process tower
DE19624433C1 (de) * 1996-06-19 1997-12-11 Daimler Benz Ag Reformierungsreaktor, insbesondere zur Wasserdampfreformierung von Methanol
JP5051769B2 (ja) * 2004-05-07 2012-10-17 タレスナノ ナノテクノロジアイ ゼットアールティー． 連続流動実験室用水素化装置及び当該装置を使用する実験室用水素化方法
HU227094B1 (hu) * 2004-08-23 2010-06-28 Thales Nanotechnologiai Rt Patronreaktor áramlásos üzemû laboratóriumi hidrogénezõberendezéshez
JP2007290987A (ja) * 2006-04-24 2007-11-08 Sumitomo Chemical Co Ltd クロロチオールホルメートの製造法

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US1631162A (en) * 1924-04-25 1927-06-07 Griscomrussell Company Vertical film-type evaporator
US2165490A (en) * 1936-12-10 1939-07-11 Nat Aniline & Chem Co Inc Gas absorption
US2696465A (en) * 1951-01-22 1954-12-07 Arthur E Kittredge Thermocompression distilling plant
NL92506C (es) * 1952-11-19
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US3356125A (en) * 1964-12-02 1967-12-05 W L Badger Associates Inc Feeding and liquid by-passing method for falling film, multiple effect evaporators
US3787188A (en) * 1971-11-26 1974-01-22 Dow Chemical Co Apparatus for catalytic reactions
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US4012405A (en) * 1975-11-28 1977-03-15 Stauffer Chemical Company Production of ethyl chlorothioformate
JPS5929521B2 (ja) * 1980-02-20 1984-07-21 チッソ株式会社 精製塩酸の製造法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004020082A1 (en) * 2002-09-01 2004-03-11 The University Of Waikato Reaction process

Also Published As

Publication number Publication date
KR900008117B1 (ko) 1990-10-31
AU3512384A (en) 1985-05-16
KR850004106A (ko) 1985-07-01
YU187584A (en) 1988-04-30
NZ210119A (en) 1987-03-06
IN162240B (es) 1988-04-16
JPS60118231A (ja) 1985-06-25
CA1212524A (en) 1986-10-14
DK158875C (da) 1990-12-31
ATE27411T1 (de) 1987-06-15
DD231296A5 (de) 1985-12-24
HUT35550A (en) 1985-07-29
SU1376938A3 (ru) 1988-02-23
AU568692B2 (en) 1988-01-07
ZA848654B (en) 1985-07-31
YU45674B (sh) 1992-07-20
AR242134A1 (es) 1993-03-31
PT79462A (en) 1984-12-01
IL73436A (en) 1988-05-31
PH21356A (en) 1987-10-15
HU197855B (en) 1989-06-28
MX165645B (es) 1992-11-25
RO90519A (ro) 1986-10-30
EP0142103A1 (en) 1985-05-22
ES8603287A1 (es) 1985-12-16
US4551325A (en) 1985-11-05
JPH0125615B2 (es) 1989-05-18
PL144228B1 (en) 1988-04-30
ES537412A0 (es) 1985-12-16
IL73436A0 (en) 1985-02-28
PL250303A1 (en) 1985-07-16
DK158875B (da) 1990-07-30
DK525784D0 (da) 1984-11-05
BR8405634A (pt) 1985-09-10
DK525784A (da) 1985-05-08
DE3463902D1 (en) 1987-07-02

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